Because of its improved characteristics including weather resistance, electrical properties, compression set, heat resistance, and low-temperature resistance, silicone rubber is widely used in a variety of fields including electronic equipment, automobiles, buildings, medical and food fields. Illustrative applications include rubber contacts used as rubber contact keys in remote controllers, type writers, computer keyboards, and musical instruments, building gaskets, rolls in copiers and printers (e.g., fixing rolls, developing rolls, transfer rolls, charging rolls, and paper feed rolls), vibration dampers in audio equipment, and compact disc packing in computers. As the demand for silicone rubber is increasing, the high productivity manufacture of silicone rubber at a low cost is desired.
The continuous preparation of organopolysiloxane is effective to meet such needs. JP-A 53-99300 corresponding to U.S. Pat. No. 4,128,568 discloses a process for continuously preparing a highly viscous organopolysiloxane in the presence of a basic and/or acidic reaction catalyst. It is described that viscous organopolysiloxanes having a viscosity of 10 to several millions of centipoises can be prepared, but no reference is made to organopolysiloxanes having a higher viscosity, that is, in the gum region. The catalysts used therein require a post-treatment for neutralization, which is cumbersome.
Another process for continuously preparing an organopolysiloxane gum is disclosed in JP-A 60-202124 corresponding to U.S. Pat. No. 4,551,515, which uses a neutralizing agent in a sufficient amount to neutralize the polymerization catalyst. This process is complicated and yields as a by-product the neutralization salt which must be disposed of and can have a detrimental influence on the product quality if left behind.
The terminal unit structure of organopolysiloxane depends on the structure of a terminal stopper used in the polymerization process. However, the process for preparing organopolysiloxane generally has the drawback that a trace amount of water in the reactant can also function as the terminal stopper. The resulting organopolysiloxane has hydroxyl groups introduced into the terminal unit, departing from the desired terminal unit. When such a high molecular weight organopolysiloxane gum having terminal hydroxyl groups is mixed with a reinforcing agent such as silica to formulate a silicone rubber compound, the compound gives rise to a crepe hardening phenomenon with the lapse of time because of the interaction between hydroxyl groups at the end of organopolysiloxane gum and hydroxyl groups on silica surface. Prior to use, the silicone rubber compound having undergone crepe hardening must be restored to the initial state by applying strong shear forces in a twin-roll mill or another kneader.
In the application where organopolysiloxane gum is used as a base component of a silicone rubber compound, it is desired to design the organopolysiloxane gum such that its terminal unit consists of a triorganosilyl group. Nevertheless, in the currently available gums, hydroxyl groups are introduced in the terminal unit owing to incidental factors as mentioned above. For the preparation of organopolysiloxane gum, it was needed to reduce the content of hydroxyl groups.
One process for reducing the hydroxyl group content is disclosed in the above-referred JP-A 60-202124. For removing a trace amount of water from the starting reactants such as a cyclopolysiloxane and a low molecular weight, linear organopolysiloxane as the terminal stopper, the reactants are previously dried using a desiccant such as molecular sieve. However, such pretreatment adds to the number of steps and renders the overall process complicated.
Another technique of reducing hydroxyl groups in organopolysiloxane terminal units is by adding a triorganohalosilane and a hexaorganodisilazane for neutralizing the alkali catalyst as disclosed in JP-A 60-49033 corresponding to U.S. Pat. No. 4,563,513. This technique is successful in reducing hydroxyl groups, but increases the number of steps and raises the problem of metal equipment corrosion due to the use of halosilane.
Therefore, for the preparation of organopolysiloxane gum (or organopolysiloxane having a high degree of polymerization), it is desired to have a more efficient technique capable of effectively reducing the content of hydroxyl groups in the terminal unit.